Oxygenated derivatives of thujopsene

ABSTRACT

There are provided novel oxygenated pentamethyldecalins and dehydro derivatives thereof which are lasting odorants of woody character and which are useful in the perfumery art. These novel compounds are prepared by oxidation of cisthujopsene and cis-dihydrothujopsene which are readily available products of natural origin.

United States Patent Shaffer et al.

[ Oct. 21, 1975 OXYGENATED DERIVATIVES OF TIIUJOPSENE [75] Inventors:Gary W. Shaffer; Garry C.

Kitchens, both of Wayne; Kent Kaiser, Pequannock, all of NJ.

[73] Assignee: Givaudan Corporation, Clifton, NJ.

[22] Filed: June 25, 1970 [21] Appl. No.: 49,950

[52] US. Cl. 260/586 P; 252/522; 260/348 C; 260/3485 L; 260/488 B;260/586 E; 260/617 F; 260/666 PY [51] Int. Cl. C07C 45/04; C07C 49/44[58] Field of Search 260/587, 586 P, 586 E [56] References Cited UNITEDSTATES PATENTS 3,268,589 8/1966 Rowland 260/587 X FOREIGN PATENTS ORAPPLICATIONS 331,509 4/l903 France 260/587 10,535 1897 United Kingdom260/587 OTHER PUBLICATIONS Appell et al., J. Chem. Soc., Vol. 1959, pp.3322-3332, (1959).

Beilstern, Handbuch der Organische Chemie, Vol., VII Syst. No.620/I-Il72, p. 677, Supplement III.

Primary Examiner-Norman P. Morgenstem Attorney, Agent, or FirmThomasCifelli, Jr.

[5 7 ABSTRACT 4 Claims, No Drawings OXYGENATED DERIVATIVES F THUJOPSENEDESCRIPTION OF THE PRIOR ART 5 i Cis-thujopsene, the starting materialin the present (VI) (1) inventon is a readily available natural product.It may The reactants are taken up in an anhydrous reaction be reduced tocis-dihydrothujopsene by methods well inert polar solvent and treatedwith an excess of oxiknown in the art. (Erdtman and Norin, Acta. Chem.dant, suitably of the chromate species at moderate tem- Scand., 13, H24(1959); Forsen and Norin, ibid, l5, peratures. 592 (1962); Norin, ibid,15, 1676 (l96l); Erdtman The following flow chart illustrates the methodstartand Norin, Chem. and Ind., 622 (1960). ing with cis-thujopsene (V)Thujopsan-Z-one, similarly a starting material herein In thismodification cis-thujopsene (V) is taken up in is prepared by oxidationof cis-thujopsene according to 40 a suitable solvent and irradiated inthe presence of oxythe method of Ohloff and Strickier (German Applicagenand a carrier dye. The color of the dye should be tion 1,91 1,440), andof S. P. Acharya and H. C. Brown the complement of at least a portion ofthe wavelength (5th International Symposium of the Chemistry of Natrangeof the irr i i n source. that i o y h dye ural Products, London, July8-19, 1968, p. 294). should absorb light in that wave length range.

After irradiation the product is reduced with a chemical (ie notcatalytic) reducing agent to yield intermedi- SUMMARY OF THE INVENTIONate enol (XIV). Enol (XIV) is then contacted with a surface activecatalyst such as alumina, or the like which is believed to cause theenol (XIV) to give the ketoform (XV) which is then rearranged to yieldthe pentamethyloctalone (I). This rearrangement is conveniently achievedby eluting the enol (XIV) from a column packed with the catalyst. Theeluant should be sufficiently polar to achieve elution within areasonable number of column volumes but not so polar as to cause Thepresent invention concerns the conversion of the readily availablenatural product cis-thujopsene (V) and its close derivativecis-dihydrothujopsene (VI) into three novel ketones and one epoxide ofrelated structure and similar olfactory activity.

Cis-dihydrothujopsene (VI) is conv rt d i d 4 elution which is too rapidto permit proper contact with 5,6,7,8,8ahexahydro-3,4a,5,5,8a-pentamethyl-2( lH)- the catalytic material.napthalenone (I) referred to herein b l as th pen- It will be seen thatthe unisolated keto intermediate tamethyloctalone (I) by two differentroutes. The same is in fact j p which is a readily compound may also bprepared starting i h i available product. Hence starting with thethujopsanthujopsene (V) and also from cis-thujopsan-Z-one 2-0116, p d my be Produced y Similar (XV) by a method related to this latterroute.Contact with a Surface active Catalyst- The following flow chart (I)shows how cis- In the first method, cis-dihydrothujopsene (VI) isoxdihydrothujopsene may be converted into pentamethyl idized to thepentamethyloctalone (I). octalone (I).

= same compound H stage C I probable reaction path CHART I F V ccn 2stage A (1) E o i 1 0H 0H o0 3 1 i I I un- A i A 0 0 known v1 I III VII1x F 'x glycol neutral i x A I CH3COOOH stage o cm I \l v Q I 0H9 V V Ion VIII 0H 0 stage B 0 g 1x t 1 O Iv 0 I VII +unknown I glycol In stageA (i) cis-dihydrothujopsene (VI) is treated with a peracid in thepresence of hydrogen ion to yield a mixture of compounds indicated byformulas (I), (III) and (VII) thru (X); The reaction product isseparated from the reaction mixture, suitably by extraction with a waterimmiscible solvent. Separation of the components at this stage is notrequired.

In stage C the reaction product of stage B is treated with a strong acidin an anhydrous solvent, suitably under continuous distillation toremove the water/solvent azeotrope.

Compound (I) and Compound (III) are unchanged, while the3-hydroxypentamethyloctahydronapthalene (VII) is converted into thepentamethylhexahydronapthalene (XI), and a 3-,hydroxy-l,2-epoxy-pentamethyldecalin (IX) is converted into compound I.

The ratio of the products I: III: XI is of the order of 25:10:]. Thisresult is most surprising since (I) and (XI) would not normally beexpected to be formed in this reaction series. The three identifiedcompounds I, (III) and (XI) constitute ca 80% of the recovered prod-UCI.

In an alternative procedure cis-dihydrothujopsene (VI) is reacted withneutral peracid, that is to say peracid having substantially no hydrogenions present, to form cis-decahydro-l,2-epoxy--2,4a,8,8,8a-pentamethylnapthalene (IV), hereinafter referredto as the epoxypentamethyldecalin (IV). This may then be converted instage A (ii) to the same products as above by the same means.

As mentioned in connection with step A (ii) above, cis-dihydrothujopsene(VI) is readily converted into the corresponding l,2-epoxide (IV) by aperacid in neutral conditions.

III

The epoxide (IV) upon treatment with an acid, suitably in anhydrousconditions in an inert atmosphere yields the pentamethyl-l-decalone(III).

The pentamethyl-Z-octalone (I) may be hydrogenated to give thecorresponding pentamethyl-Z- decalone, i.e.: cis-3 ,4,4a,5,6,7,8,8a-octahydro- 3,4a,5,5,8a-pentamethyl-2-(1H)-napthalenone (II).

It has been found that compounds I, II, III and IV have valuableproperties as odorants in perfume manufacture. The compounds havevarious woody odours which add body and strength to the odorantcompositions to which they are added. They possess valuable fixativeproperties and possess very useful tenacity.

DESCRIPTION OF THE PREFERRED EMBODIMENTS Cis-dihydrothujopsene (VI) isoxidized to pentamethyloclatone (I).

In the preferred modification cis-dihydrothujopsene (VI) is taken up ina suitable polar reaction inert anhydrous solvent. It is preferred touse an aliphatic acid and anhydride such as an alkanoic acid andanhydride. The especially preferred alkanoic moities contain 1-5 carbonatoms such as the formic, acetic, propionic, butyric and valericmoieties, however in view of the malodorous properties of certain of themoieties, acetic and propionic acids and anhydrides are the solvents of.choice. i

There is utilized as an oxidant any available oxidant of the chromatespecies, especially preferred are the alkali metal dichromates and thealkylchromates such as sodium or potassium dichromate or, for exampletbutylchromate.

There is utilized at least the calculated amount of oxidant (i.e. 4equivalents of oxidant per mole of (VI) however it is preferred to usean excess of oxidant, a two fold excess (ie 12 equivalents per mole of(VI) is especially preferred. The concentration of (VI) lies between0.25 and 0.5 moles/litre of solvent.

The reaction is exothermic. It is therefore preferable to add theoxidant slowly while maintaining the vessel temperature at or below 25C.After thorough mixing of the reagents the temperature is carefullyraised. The temperature may rise to 50C, however it is preferred to holdthe temperature between 30 to 40C in which range the reaction is selfsustaining and will decline upon completion of the reaction. Whilereaction times will of course vary, generally the addition step shouldtake about 1.5 hours, the stirring step at 25 about 0.5 hours and thereaction step at 40 about 2-5 hours.

The reaction is then quenched and the product isolated. Suitably thereaction mixture is poured into an approximately equivalent volume ofwater and extracted with a suitable water immiscible solvent and thesolvent removed by evaporation.

In the irradiation process using cis-thujopsene (V) as startingmaterial, the thujopsene (V) is taken up in any commonly utilizedirradiation solvent. Among these solvents may be included hydrocarbons,ethers, alcohols and the like. However alkanols such as methanol beingespecially preferred.

The irradiation solution is sparged with oxygen, preferably through asintered glass plate. The source of oxygen may be pure oxygen or air.The rate of flow is not critical, flow rates of between I and 30 litresper minute have been found satisfactory.

The irradiating source may comprise principally visible light (450-700nm) or U.V. light (200-450 nm).

With visible light there are used carrier dyes whose colour is acomplement of at least a portion of the irradiated wave length range ofthe irradiation source. As long as these criteria are met, the actualcarrier dye used is not critical, however rose bengal, eosinchlorophyll, methylene blue and the like have been found useful.

Where U.V. light is used sensitizers such as benzene,

aryl and alkyl ketones or other aromatics may be employed, however theuse of high energy sources such as U.V. light is not favored.

The irradiation is carried out between 0 and 50C, suitably at between2025C. Irradiation is continued until oxygen uptake ceases. This isdetermined by a steady, non-increasing value in a hydroperoxidedetermination.

The irradiated mixture is then reduced, any reducing agent may be used,aqueous sodium sulfite, lithium aluminum hydride and sodium borohydrideare especially suitable. It should be noted however that where thesolvent used is a hydroxylic solvent, lithium aluminum hydride is notsuitable. After addition of the reducing agent, more water is added andthe product, presumably the enol (XIV) among othrs is extracted with asuitable water immiscible solvent. The residue obtained ischromatographed on a suitable catalyst.

The catalyst should preferably be neutral alumina, acidic or basicalumina are operative but the yields are not optimal. The catalyst ofchoice is neutral grade I alumina.

The polarity of the solvent used is important but not totally critical.It should be more polar than hexane and less polar than methanol.Hexane/benzene gives byproducts while benzene/ether preferably at a 4:1ratio gives the desired pentamethyloctalone (I).

While the column ratio is not critical good results have been obtainedat a load/column ratio of 1:50 to 1:100.

In accordance with the foregoing catalytic chromatographic procedure,but starting with thujopsan-2-one (XV), the same product is obtained. Itshould be noticed however that solvents of slightly higher polarity arerequired to elute the pentamethyloctalone (I).

In the fourth modification of the procedures for the preparation ofpentamethyloctalone (I), cisdihydrothujopsene (VI) is treated withperacid in the presence of hydrogen ion. There may be utilized anyperacid, suitably an organic peracid such as peracetic, perphthalic,perbenzoic or methachloro perbenzoic acid. Commercial peracetic acidcontains 1% of concentrated sulfuric acid, if other peracids are used, asimilar quantity of acid must be added. The quantity is not critical,from 0.2-5% of acid may be added.

While it is preferred to carry out the reaction without solvents, theremay be utilized reaction, inert solvents such as benzene, ether, glacialacetic acid or the like.

The reagent medium of choice is 40% aqueous peracetic acid.

There is utilized an excess of peracid, while there is no upper limit tothe amount of acid used, it is preferred to use at least 2-3 moles ofperacid per mole of dihydrothujopsene (VI).

The acid is warmed with agitation at a temperature of between 10 and C,preferably at between 30 and 40C for l060 mins. preferably for about 20minutes while the dihydrothujopsene (VI) is added slowly. After additionis complete, agitation at this temperature is continued for about 3hours, although longer times may sometimes be required to remove thestarting material. The reaction mixture is then quenched with water andextracted, suitably with hexane.

The residue from the extraction step is taken up in an alkanol. suitablyin methanol and treated with a base, suitably an alkali, such as sodiumor potassium hydroxide.

There is utilized from l-5, suitably about 2 parts by weight of solventrelative to each part of peracid product.

There are utilized 1-5 moles of base per mole of residue, preferablybetween 1.5-2 moles/mole are used.

While it is not essential to heat the reaction mixture, temperaturesbetween 25 and 100C or even higher are operative. It is especiallyconvenient to carry out the reaction at the reflux temperature of thesolvent. The reaction is run until all of the ester has been saponified,as determined by infrared analysis, 3 hours is usually sufficient forthis to occur.

The reaction product is then isolated. In the preferred mode ofisolation water is added to the reaction mixture and methanol removed bydistillation until a pot-temperature of about 95C is reached. Themixture is then cooled and extracted with a water-immiscible solvent,hexane being especially suitable. The hexane extract is worked up in theusual manner to leave a saponified residue.

The saponified residue is taken up in a hydrocarbon solvent, preferablya solvent which forms an azeotrope with water such as benzene, tolueneor the like. There is added thereto a strong acid, mineral acids ororganic acids may be employed, for example sulfuric acid or ptoluenesulfonic acid may be used.

There is employed at least 1 part by weight of solvent per part byweight of saponified residue.

Preferably there are used 2-3 parts by weight of solvent for part ofresidue.

There are utilized between 1 and by weight of acid relative tosaponified residue, suitably there are used 4% by weight of acid.

The mixture is heated under reflux until no more azeotrope is formed. 10hours is usually sufficient for completion of the reaction.

The reaction mixture is then worked up. In the preferred method the acidis washed out with aqueous sodium bicarbonate, the solvent removed by anevaporation and the residual oil distilled under reduced pressure. Thedistillate is then further purified, suitably by column chromotography.

The pentamethyloctalone (I) may be hydrogenated to give thecorresponding pentamethyldecalone (II).

The hydrogenation is carried out in a solvent in the presence of acatalyst. Any solvent resistant to catalytic hydrogenation, which willnot poison the catalyst may be used. Thus alkanols such as ethanol, andthe alkanoic acids such as acetic acid and the like may be utilized.Glacial acetic acid is especially preferred since good results may beobtained at room temperature, while other solvents require heating toabout 40-70C.

Any hydrogenation catalyst may be used, among them may be mentionedpalladium, platinum, platinum oxide, Raney nickel, etc. with or withouta carrier. Especially preferred however is palladium on charcoal,suitably 5% palladium on charcoal at a ratio of 2-l0g, preferably about5g of catalyst/mole of octalone charged. The reaction is run at -100 psisuitably at about 40 psi. Any temperature may be used up to 100C, whereglacial acetic acid is used as the solvent, the reduction is carried outat ambient temperature.

The hydrogenation is run until no further hydrogenation occurs.

The product was then isolated. The hydrogenation mixture is filtered,and the filtrate evaporated to yield the decalone (II) in crystallineform.

The cis-dihydrothujopsene(VI) may be oxidized to the corresponding1,2-epoxy pentamethyldecalone (IV) which in turn is rearranged to yieldthe corresponding pentamethyl-l-decalone (III).

In the process the cis-dihydrothujopsene (VI) is taken up in a solvent,such as a hydrocarbon solvent preferrably hexane: There added a neutralperacid such as peracetic, perchlorobenzoic, perbromobenzoic,perbenzoic'or perchloroacetic acid.

Where the commercially available peracid contains an acidic stabilizer(i.e.1% sulfuric acid in peracetic acid) this must be removed.

The easiest method of removing the excess hydrogen ion is by addition ofthe salt of a weak acid suitably an acid having a pH of 3-6. Especiallysuitable is sodium acetate. In order to neutralize the excess acid,there are added 2 moles of the salt/mole of strong acid present, itispreferred however to use twice this amount.

There is utilized at least one mole of peracid per mole ofcis-dihydrothujopsene (VI) preferably 1-1 .5 mole of preferably 40%aqueous peracid.

The use of a solvent in the reaction is optional, where a solvent isused, a hydrocarbon solvent such as hexane is preferred.

The reaction is carried out at moderate temperatures suitably between050C, although higher temperatures are permitted. It is preferred to runthe reaction at between about 30-40C for about 15 to 30 hours,preferably for about 20 hours.

The reaction is quenched with water, the hexane and water layersseparated and the aqueous layer extracted with hexane. The combinedhexane extracts are washed with aqueous sodium bicarbonate and then withaqueous sodium hypo-sulfite, and water. Evaporation and distillationunder reduced pressure yields the desired epoxypentamethyl decalin (IV).

The epoxide (IV) is rearranged to the corresponding ketone (III) bymeans of acid in a solvent.

As acids there may be used minerals acids such as sulfonic, phosphoricor perchloric, organic acids such as sulfonic, phosphoric or perchloric,organic acids such as p-toluene sulfonic acid, Lewis acids such as borontrifluroide, or aluminum chloride. Catalysts such as magnesium bromideor magnesium iodide may also be employed. The reaction is preferablycarried out in a solvent, any anhydrous solvent used in Friedal-Craftsreactions may be used. Especially preferred is the use of aluminumchloride in petroleum ether as the rearranging agent and solvent.

The quantities of acid utulized are not critical, however in order toachieve an acceptable rate of reaction these are utilized between 1 and1.3 moles of aluminum chloride per mole of epoxide (IV). While thereaction may be run at temperatures between about 0 and 50C,temperatures of between about 20 and 30C are especially convenient.Reaction is usually complete in between about 15 and 30 minutes. Thereaction is then quenched. Quenching is suitably achieved by cooling toice bath temperatures and adding dilute aqueous sulfuric acid to thereaction mixture.

The reaction mixture is then worked up in the usual manner and thepentamethyldecane-l-one (III) is purified by distillation under reducedpressure.

EXAMPLE 1 Cis-4a,5,6,7,8,8a-hexahydro-3,4a,5,5,8a-pentamethyl- 2(1H)-napthalenone (I).

A mixture of 103 g (0.50 mole, 2.0 eq) of dihydrothujopsene (VI), 700 mlacetic anhydride and 250 ml glacial acetic acid was stirred at roomtemperature and over a period of 1% hrs. was added at 25, using ice bathcooling when necessary, 300 g (1.0 mole, 6.0 eg) of sodium dichromatedihydrate. After the addition, the mixture was stirred at 25 for 1: hr.,using ice bath cooling when necessary, then carefully heated to 40 andmaintained at 40 for 2% hrs. with ice bath cooling when necessary.

The mixture was allowed to cool and poured into a mixture of l l. ofwater and 300 ml of toluene. The layers were separated and the aq. phaseextracted with toluene (2 X 300 ml). The combined toluene extract wasbackwashed with sat. salt solution (3 X 250 ml), dried over magnesiumsulfate, and concentrated under reduced pressure.

The residual oil was distilled under nitrogen through a inch glasshelices packed column at 0.5 mm pressure. The first fraction (bp 72-95)was recovered dihydrothujopsene (VI) plus two minor oxidation byproducts(15.95 g), the second fraction (bp 99101) was the desiredcis-4a,5,6,7,8,8a-hexahydro- 3,4a,5,5,8a-pentamethyl-2( lH)-napthalenone(I) (95% pure), 64.0 g (58% yield); n,, 1.5 178; mol wt. 220 (massspectrum, neat max., 1675 (s), 1640 (w), 1384 (m), 1367 (m), 1117 (w)cmkk MeOH max. 243 nm (6 7,180); nmr (1', ppm, CDCl 3.50 (1H, quartet, J1.5 Hz, vinylic H), 7.49 and 7.84 (2H, AB quartet, J 17.5 Hz, H a tocarbonyl), 8.22 (3H, doublet, J 1.5 Hz, vinylic methyl H), 8.58 (6H,broad absorption, methylene H), 8.91 and 8.99 (12H, two singlets, methylH). The nmr assignments were confirmed using both 60 and 100 MHzspectra. Anal. Calcd. for C H O: C, 81.76; H, 10.98. Found: C, 81.53 H,11.01.

EXAMPLE II Cis-4a,5,6,7,8,8a-hexahydro-3 ,4a,5,5 ,8a-pentamethyl-2(1-H)-naphthalenone (I).

A solution of 50.0 g (0.245 mole) of thujopsene (V), 1.0 g rose bengal,and 1450 ml of distilled methanol was aerated with oxygen at 4 l./min.and irradiated with 6-15 watt green-photo GE fluorescent bulbs until theuptake of oxygen ceased as monitored by a hydroperoxide determination.

The red solution was added dropwise with slight cooling to a stirredsolution of 70 g sodium sulfite in 500 ml of water. The solution wasstirred overnight at room temperature, then at 70-80 for 2 hrs., allowedto cool, diluted with 500 ml of water, and partially concentrated underreduced pressure.

The mixture was diluted with 500 ml of water and 200 ml of ether. Thelayers were separated, the aq. phase extracted with ether and theetherial extract was backwashed with sat. salt solution, dried,filtered, and concentrated.

A portion (10.0 g) of the crude mixture (46.6 g) was chromatographed on350 g of alumina (neutral, act. 1)

packed with hexane into a 2.5 X 67 cm column. Elution naphthalenone (I),1.43 g (12l/2% yield); the physical and spectral data was identical tothat described in Example 1.

EXAMPLE III Cis-4a,5 ,6,7,8,8a-hexahydro-3,4a,5,5 ,Sa-pentamethyl- 2(1H)-naphthalenone (l).

Thujopsan-Z-one (XV) (1.0 g) was charged onto g of alumina (neutral,activity I) packed with benzene into a 1.5 X 50 cm column. Elution withbenzene-ether mixtures and then with pure ether gave pure cis-4a,5,6,7,8,8a-pentamethyl-2( 1H )-naphthalenone (I) (0.197 g) andelution with ether-methanol 50:1 eluted a mixture of pentamethyloctalone(I) (0.248 g, 45% overall yield) and unreacted thujopsan-2-one (XV)(0.315 g, 32%). The pentamethyloctalone I gave physcial and spectraldata identical to that described in Example 1.

EXAMPLE IV Cis-4a,5 ,6,7,8,8a-hexahydro-3,4a,5,5 ,8a-pentamethyl-2(1H)-naphthalenone (I).

The pentamethyloctalone (I) was prepared by the sequential applicationof the three following procedures:

A. Into a 500 ml reaction flask equipped with an agitator, thermometer,dropping funnel and a condenser was charged 125 g of peracetic acid(40%, stabilized with 1% H 80 and while agitating heated to 35C.Dihydrothujopsene (VI) (51.2 g) was fed in while agitating at 30C over a20 minute period and the batch agitated at 35C for 3 hours. Water wasadded (250 ml) and the batch extracted with 3 X 50 ml of hexane.

The hexane solution was washed as follows: 2 X 50 ml of water, 1 X 50 mlof 10% NaHCO solution, 1 X 50 ml of water, 1 X 50 ml of 10% Na S Osolution and l X 50 ml of water. The hexane was removed by distillationunder reduced pressure leaving a residual oil (59 g) which analyzed byVPC (20M column, 225C) as follows: (1) 1.3%, (2) 3.0%cis-dihydrothujopsene, (3) 1.4% cis- 1,2,3,4,4a,8a-hexahydro-4,4,4a,6,8apentamethylnaphthalene (XI), (4) 0.2%,(5) 0.5% epimer ofcis-3,4,4a,5,6,7,8,8a-octahydro-2,4a,8,8,8apentamethyl-l(2H)-naphthalenone(I11), (6) 14.2% epimer ofcis-3,4,4a,5,6,7,8,8a-octahydro-2,4a,8,8,8apentamethyl-l(2H)-naphthalenone(III), (7) 6.3% epimer ofcis-l,2,4a,5,6,7,8,8a-octahydro-3,4a,5,5,8apentamethyl-Z-naphthylacetate (VIII), (8) 3.3% epimer ofcis-1,2,4a,5,6,7,8,8a-octahydro-3,4a,5,5,8apentamethyl-Z-naphthylacetate (VIII), (9) 17.9% of the desiredcis-4a,5,6,7,8,8a-hexahydro-3,4a,5,5,8apentamethyl-2( l H)-naphthalenone(l), (10) 2.4% epimer ofcis-1,2,4a,5,6,7,8,8a-octahydro-3,4a,5,5,8apentamethyl-Z-naphthol(VIII), (11) 5.4% epimer of cis-l ,2,4a,5,6,7,8,8a-octahydro-3,4a,5,5,8apentamethyl-2-naphthol (VII), (12) 2.6%cisdecahydro-l ,2,-epoxy-3-acetoxy-2,4a,8,8,8a-pentamethylnaphthalene(X), (13) 33.6% cis-decahydro-l,2-epoxy-3-hydroxy-2,4a,8,8,8a-pentamethylnaphthalene (IX), and (14) 7.5%unknown glycol.

B. The 59 g of crude material obtained as above, 10

g of potassium hydroxide, 10 ml of water and ml of methanol were chargedin a reaction flask and agitated under reflux (67C) for 3 hours. Water(250 ml) was added and the methanol was distilled at atmosphericpressure until a pot temperature of 95C was reached. The batch wasextracted u ith 3 X 100 ml of hexane and the hexane extract was washedneutral with water. The hexane was removed by distillation leaving aresidual oil (53 g) which was analyzed by VPC (20M column, 225C) asfollows: (1) 2.7% XI, (2) 2.5%, (3) 1.3%, (4) 2.4%, (5) 5.2% epimer ofIII, (6) 9.4% epimer of III, (7) 2.7%, (8) 19.3% of the desired productI, (9) 17.9% epimer of VII, 10) 4.1% epimer of VII, (11) 1.0% epimer ofIX, (12) 29.2% epimer of IV, and (13) 2.3% glycol.

C. The crude saponified mixture (53 g) obtained .in the previous stepwas agitated under reflux with 125 ml of benzene and 2 g toluenesulfonicacid for 10 hours while removing 3.2 g of water through a waterseparator. The batch was washed with 2 X 50 ml of water, 1 X 25 ml of10% NaHCO and 1 X 50 ml of water. The benzene was distilled underslightly reduced pressure leaving a residual oil (50 g) which was vacuumdistilled at 0.5 mm using a 6 inch column packed with glass helices andgave the following: (1) 6.2 g. of fractions, b.p.. 80-107C/0.5 mm., n15012-15042, (2) 37 g of fractions, b.p. 107132C/O.5 mm., n 15060-15160.Fraction 1, 6.2 g, was shown by VPC to contain besides other materials(mainly hydrocarbons) 14.5% of the diene XI, 20.1% of epimers of III and16% of the desired 1. Fraction 2, 37 g, was shown by VPC to consistbesides other materials (mainly hydrocarbons), 24.4 of epimers of IIIand 62.6% of the desired pentamethyloctalone I.

Fractions 2 (5.0 g) was chromatographed on 300 g of alumina (neutral,activity III) packed with hexane into a 2.5 X 62 cm. column. Elution,using 50 ml fractions, with hexane gave 0.33 g (7%) of hydrocarbons.Further elution with hexane and then with hexanebenzene 10:1 gave 1.65 g(33%) of a mixture of epimers of III. Continued elution withhexane-benzene 10:1 and then with hexane-benzene 1:1 gave 2.94 g (59%)of the desired pentamethyloctalone (I).

The pentamethyloctalone I gave physical and spectral data identical tothat described in Example I.

EXAMPLE V Cis-4a,5 ,6,7,8,8a-hexahydro-3 ,4a,5 ,5 ,8a-pentamethyl-v2(1H)-naphthalenone (1).

Into a reaction flask equipped with an agitator, thermometer, condenser,and a water separator was charged gcis-decahydro-3,4-epoxy-3,4a,5,5,8apentamethyl-Z-naphthol (IX), preparedas described in Example VII, 0.5 g toluenesulfonic acid and 75 ml ofbenzene. The batch was refluxed for 23 hours while removing waterthrough the separator. The batch was cooled to room temperature andwashed with 2 X 50 ml of water, neutralized with sodium bicarbonate andwashed with 2 X 50 ml of water. The benzene was removed by distillationunder reduced pressure leaving a residual 4.5 g of crude product, whichwas vacuum distilled at 0.4 mm using a micro distillation head. Thefollowing fractions were collected: (1) 0.2 g (b.p. 102C/0.4 mm., n1.5115); (2) 2.7 g (b.p. 105-123C/0.4 mm., n 1.5130), (3) 0.9 g ofresidue. Fraction 2 analyzed by VPC (225C, M) as containing 7components: (1) 0.3%, (2) 1.8%, (3) 6.7%, (4) 5.6%, (5) 76.2%, (6) 2.8%,(7 6.5%. A sample of component 5 was isolated by VPC (225C 20M) andshown by spectral data to be cis-4a,5,6,7,-8,8ahexahydro-3,4a,5,5,8a-pentamethyl-2(1I-I)- naphthalenone (I), identical to (I) prepared inExample I.

EXAMPLE VI Cis-4a,5,6,7,8,8a-hexahydro-3,4a,5,5,8a-pentamethyl- 2( 1H)-naphthalenone (I) Into a 50 ml reaction flask equipped with anagitator, thermometer, dropping funnel and a condenser was charged 2.5 gperacetic acid (40% containing 1% H 80, stabilizer). The batch wasagitated and heated to 35C and 2.2 g ,of epoxydihydrothujopsene (IV), asprepared in Example IX, was added over a 25 minute period at 35C and thebatch agitated at 35C for 3% hours. The batch was diluted with water andextracted with 2 X 50 ml of benzene. The benzene extractwas washed withwater, washed with 10% sodium bicarbonate, and then'washed with wateruntil neutral. The benzene was removed by distillation under reducedpressure leaving a residual crude of 2 g which analyzed by VPC (20Mcolumn, 225C) as follows: (1)'0.4%, (2) 0.4% dihydrothujopsene (VI), (3)4.9% cis- 1,2,3 ,4,4a,8a-hexahydro-4,4,4a,6,8a-pentamethylnaphthalene(XI), (4) 3.0%, (5) 16%-epimer of cis-3,4,4a-5,6,7,8,8a-octahydro-2,4a,8,8,8a-pentamethyl-1(2I-I)-naphthalenone (III), (6) 16.9% epimer of cis-3,4,4a,5,6,7-8,8a-octahydro-2,4a,8,8,8a-octahydro-2,4a,8,8,8a-pentamethyl-1(2l-I)-naphthalenone (III), (7) 10.0% epimer ofcis-l,2,4a,5,6,7,8,8a-octahydro- 3,4a,5,5,Sa-pentamethyl-Z-naphthylacetate (VIII), (8) 12.5% epimer of cis-l,2-4a,5,6,7,8,8a-octahydro-3,4a,5,5,8a-pentamethyl-Z-naphthyl acetate (VIII), (9) 17.3% of thedesired cis-4a,5,6,7,8,8a-hexahydr0- 3 ,4a,5 ,5 ,8a-pentamethyl-2(1I-I)-naphthalenone (I), (10) 2.2% epimer ofcis-l,2,4a,5,6,7,8-8a-octahydro- 3,4a,5,5,8a-pentamethyl-Z-naphthol(VII), (11) 2.1% epimer ofcis-l,2,4a,5,6,7,8,8a-octahydro-3,4a-5,5,8apentamethyl-Z-naphthol (VII),(12) 4.0% cisdecahydro-l ,2-epoxy-3-acetoxy-2 ,4a,8 ,8,8a-pentamethylnaphthalene (X), (13) 21.0% cis-decahydro-1,2-epoxy-3-hydroxy-2,4a,8,8,8a-pentamethylnaphthalene (IX), and (14) 4.6%unknown glycol.

This above result is identical to the results in Example IV, which usesdihydrothujopsene (VI) as the starting materiaL The material can beconverted by saponification followed by dehydration to the desiredpentamethyloctalone (I), pentamethyl-l-decalone (III) and diene (XI) asdescribed in procedure B and C of Example IV.

EXAMPLE VII cis-l.,2,4a,5 ,6,7,8,8a-Octahydro-3,4a,5,5,8apentamethyl-Z-naphthol (VII)cis-Decahydro-3,4-epoxy-3,4a,5,5,8a-pentamethyl-2- naphthol (IX) cis- 1,2,3 ,4,4a,8a-I-Iexahydro-4,4,4a,6,8a-pentamethylnaphthalene (XI) Onehundred fifty grams (150 g) of dihydrothujopsene (VI) was processed asdescribed in Example IV, section A and gave crude material, (168g) whichwas dissolved in hexane (450ml). The hexane solution cooled to C gavesolid crystals which-after filtering and air drying gave 17 g ofcrystalline IX, m.p. 140-142.5C.

A small sample of IX was recrystallized from methanol and vacuum dried.The product analyzed as follows:

m.p 143.5144.5C; saponification value after acetylation 199.1; vKBrmax., 3490 (s), 1375 (w), 1368 (s), 1355 (w), 1332 (m), 1318 (m), 1304(m), 1290 (m), 1262 (w), 1242 (m), 1230 (m), 1198 (w), 1088 (s), 1065(s), 1048 (s), 1027 (s), 1004 (s), 972 (w), 912 (m), 872 (s), 820 (m),785 (m), 702 (m), 640 (w); NMR (1', ppm,CDCl ),6.15 1H, triplet, J=7, aHto OH), 6.97 (1H, singlet, epoxide H), 8.00 (2H, broad, BH to C-OH),8.62 (3H, singlet, epoxide methyl), 8.95 (3H, singlet,CI-I 8.98 (3Hsinglet, CH 9.06 (6H, singlet, 2CH 8.5 4 9.0 (6H, multiplet, 3CH Massspectra, 220 ion which is M-18 (H O). Anal. Calcd. for C H O C, 75.58;H, 11.00. Found: C, 75.55; H, 11.03.

The hexane was removed by distillation at atmospheric pressure and theresidue (151 g) was vacuum distilled at 0.6 mm using a distillation headand gave the following: (1) g of fractions(b.p. 85140C/0.6 mm., mainlyhydrocarbons), (2) 114.5 fractions (b.p. 140-155C/0.6 mm.),and (3) 11.0g residue. The 1 14.5 g fractions on standing partially crystallized.The crystals were filtered and washed with cold hexane. The driedcrystals amounted to 19 g, 140142.5C and were identical to compound IXabove.

The mother liquor from the crystals was distilled under vacuum to removethe hexane and the residual material (saponification value 85.9) wassaponified by refluxing for 6 hours with 15 g potassium hydroxide, 15 mlof water and 100 ml of methanol. The reaction was worked up as describedin Example IV section B and gave 77 g of crude material which was vacuumdistilled at 0.6 mm using a 6 inches column packed with glass helicesand the following fractions collected: (1) 29.0 g (b.p. 96-105C/0 .6mm), (2) 31.8 g (b.p. 105-115C/0.6 mm) (3) 10.2 g (b.p. 115-127C/0.6 mm.Fractions 2 and 3 partially crystallized on standing. Recrystallizationfrom hexane of the crystals (6.9 g) from fraction 2 gave pure VII whichanalyzed as follows: m.p. l22-123C; mol. wt. 222 (mass spectrum); KBrmax., 3220 (s), 1395 (m), 1380 (s), 1365 (m), 1333 (m), 1280 (s), 1195(w), 1122 (w), 1090 (m), 1075 (m), 1055 (s), 1040 (m), 1012 (s), 978(w), 960 (w), 932 (m), 900 (w), 853 (m), 802 (w); NMR (7', ppm,CDCl 4.55(1H, singlet, vinylic H), 5.98 (1H triplet, J=6.5 Hz,Ha to C-OH), 8.27(3H, singlet, vinylic CH 8.97 (3H, singlet CH 9.00 (3H, singlet, CH 9.05(6H, singlet, 2CH 8.38-8.90 (8H, multiplet, 4CH

Fractions 1, 3, and the mother liquid from fraction 2 above werecombined and 51 g of this material was refluxed with 125 ml of benzeneand 2.0 g p-toluenesulfonic acid for 12 hours while removing waterthrough a water separator. The batch was worked up as described inExample IV, section C., and gave 50 g of crude material which was vacuumdistilled at 0.5 mm using a 6 inches column packed with glass helicesand the following fractions collected: (1) 2.0 g (b.p. 80C/0.5 mm.), (2)13.5 g (b.p. 80-105C), (3) 26.5 g (b.p. l05-116/0.5 mm.) and 7.0 g ofresidue. Fraction 1 was pure cis-l,2,3,4,4a-8a-hexahydro-4,4,4a,6,8a-pentamethylnaphthalene (X1) and fraction 2 was principallycis-l,2,3,4,4a,8a-hexahydro- 4,4,4a,6,8a-pentamethylnaphthalene (XI).

Fraction 1 (X1) analyzed as follows: mol. wt. 204 (mass spectrum); vneatmax., 1654 (m), 1382 (s), 1373 (s), 1363 (m), 1340 (w), 1180 (w), 1117(w), 1078 (w), 1025 (m), 970 (m), 845 (m), 826 (m), 745 (m), 735 (s);NMR (r,ppm,CDCl )centered at 4.47 (2H, multiplet, 2 vinylic H), centeredat 4.94 1H, W"/, 5H2, vinyl H), 8.28 (3H, doublet J=1.5 Hz, vinylic CH8.97 (3H, singlet, CH 9.00 (3H, singlet, CH 9.12 (3H, singlet, CH 9.18(3H, singlet, CH

8.458.85 (6H, multiplet, 3CH

shown by IR and NMR that A and B were epimers of pentamethyl-l-decalone111, Example X, and C was pentamethyloctalone 1, Example 1.

EXAMPLE VIII Cis-3,4,4a,5,6,7,8,8a-octahydro-3,4a,5,5,8apentamethyl-2-(1H)-naphthalenone (II) A mixture of 17.7 g (0.0805mole) of pentamethyloctalone I, ml of glacial acetic acid, and 0.5 g of5% palladium on carbon was hydrogenated at room temperature on a Parrshaker under an atmosphere at 40 psi of hydrogen until the hydrogenuptake ceased. The solvent was removed under reduced pressure and thecrude crystalline material (18.7 g) was recrystallized twice frommethanol to give cis-3,4,4a,5,6,7,8,8aoctahydro-3,4a,5,5,8a-pentamethyl-2-( 1H)- naphthalenone (II) as white needles, 8.45 g (50yield); mp 11l.01l3.5; mol. wt. 222 (mass spectrum) vKBr max. 1700 (s),1440 (s), 1368 (m), 1356 (w), 1232 (w), 1184 (w), 1124 (w), 1096 (w),cm; NMR (1', ppm, CDCI 60 MHz), 7.12-8.00 (3H, multiplet, H alpha to thecarbonyl), 8.01-8.74 (8H, multiplet, methylene H), 8.79, 8.88, 8.90, and9.14 (four singlets, four tertiary methyl groups), 9.02 (doublet, J= 6Hz, secondary methyl group). The total methyl region integrated for 15H.Anal. Calcd. for C H O: C, 81.02; H, 11.79. Found: C, 80.99; H, 11.93.

EXAMPLE IX Cis-decahydro-l ,2-epoxy-2,4a,8,8,8a-pentamethylnaphthalene(IV).

Into a reaction flask equipped with agitator, thermometer, and droppingfunnel was charged g of dihydrothujopsene (VI), 300 ml hexane and 50 ganhydrous sodium acetate. The batch was agitated and heated to 40C and172 g peracetic acid (40%) was fed in over a hour period at 40C. Thebatch was agitated at 40C for 17 hours. Peracetic acid (30 g) was addedand agitation continued 3 hours at 40C.

300 ml of water was added and the hexane and aqueous layers separated.The aqueous layer was extracted with 3 X 100 m1 of hexane. The combinedextract was washed with 1 X 100 ml of water, neutralized with 10% NaHCOwashed with 1 X 100 ml of 10% Na S O and washed with 1 X 50 ml of water.The hexane was removed under reduced pressure and the crude material(160 g) distilled on a 37 cm column packed with glass helices to givethe following fractions: (1) 15.2 g (b.p. 7476C/0.5 mm., 51%dihydrothujopsene (VI), 49% cis-decahydro-l ,2-epoxy-2,4a,8,8,Sa-pentamethylnaphthalene (IV), (2) 32.0 g (b.p. 76C/0.5 mm., 20%dihydrothujopsene (V1), 80% cis-decahydro-l,2-epoxy-2,4a,8,8,8a-pentamethylnaphthalene (IV), (3) 92.9 g (b.p.7681C/0.5 mm.) of the desired cisdecahydro-l,2-epoxy-2,4a,8,8,8a-pentamethylnaphthalene (IV), (4) 8.3 g (b.p.81-83C/0.5 mm., 80% cis-decahydro-l,2-epoxy-2,4a,8,8,8a-pentamethylnaphthalene (IV)), (5) 5.0 g of residue.

The cis-decahydro-l ,2-epoxy-2,4a,8,8,8a-pentamethylnaphthalene (IV)(90.5% yield) analyzed as follows: n 1.4965; sp.gr.25C/25C: 0.9787; VPC(20M column, 225C) two components, (1) 5.5%, (2) 94.5%; mol. wt. 222(mass spectrum). Anal. Calcd. for C I-1 0: C,81.02, H, 11.79; Found: C,81.21, H, 11.74.

The two components of the epoxypentamethyldecalin IV were separated in apure form by VPC (210C, 20M column). The minor isomer analyzed asfollows: mol. wt. 222 (mass spectrum); 11 neat max. 1395 (s), 1378 (s),1370 (s), 1245 (m), 1210 (m), 1110 (m), 1046 (m), 1037 (m), 1020 (m),962 (w), 940 (w), 918 (m), 886 (s), 815 (s), 762 (w), 705 (w), 582 (m);NMR (1',ppm,CDCL ),7.33 (1H, singlet, a-l-l), 8.74 (3H, singlet, CH 8.96(6H, singlet, 2CH 9.02 (3H, singlet, CH 9.09 (3H, singlet, CH 7.65 8.70(8H, complex multiplet, 4CH

The major isomer analyzed as follows: mol. wt. 222 (mass spectrum);vneat max., 1397 (s), 1380 (s), 1334 (w), 1200 (w), 1180 (w), 1120 (w),1090 (w), 1076 (w), 1038 (w), 1005 (w), 980 (w), 945 (w), 930 (w), 920(w), 905 (w), 870 (m), 862 (m), 820 (m); NMR (1', ppm, CDCI 7.16 (1H,singlet, a-H), 8.71 (3H, singlet, a-Cl-l 8.94 (6H, singlet, 2CH 9.03(6H, singlet, 2CH

The above data shows the two compounds are epimers.

EXAMPLE X Cis-3,4,4a,5 ,6,7,8,8a-octahydro-2,4a,8,8,8apentamethyl-l(21-1)-naphthalenone (III) Into a reaction flask equipped with anagitator, thermometer, condenser, drying tube and a nitrogen inlet tubewas charged 17.7 g of aluminum chloride and 100 ml of petroleum ether.The batch was placed under an atmosphere of nitrogen and a mixture of 25g of the epoxypentamethyldecalin (1V), prepared as in Example IX, in 25ml of petroleum ether was added while agitating over a 17 minute periodat 25 to 30C with slight cooling. The batch was agitated at 25C for 1hour and cooled to -C. A solution of 300 ml of 5% sulfuric acid wasadded and agitated at 5C for /2 hour and then an additional 1% hoursallowing the temperature to rise to room temperature. The petroleumether layer was separated and the aqueous layer extracted with 2 X 50 mlof petroleum ether. The combined ether layers were washed with water,neutralized with 10% NaHCO solution and washed neutral with water. Thepetroleum ether was removed under reduced pressure leaving a residual(25 g) which was vacuum distilled at 0.5 mm. using a 6 inch columnpacked with glass helices and the following fractions collected:

(1)6 g (b.p. -88C, n 1.5015-1.5025),(2) 14.5 g (b.p. 88-120 C, n15026-15040), and 2 g of residue.

Redistillation of fractions 1 and 2 gave 4 g hydrocarbons (b.p. 8587C. n1.5018), and 16 g (b.p. 98105C, n 1.5026) of the desired product, cis-3,4,4a-5,6,7,8,8a-octahydro-2,4a,8,8,8a-pentamethyl- 1(2H)-naphthalenone (III). (Yield: 64%). Analysis: Mass Spectrum, mol.wt. 222: Calcd for C H O: C, 81.02%; H, 11.79%; Found: C, 81.08%; H,11.67%; VPC (225C, 20M column) two components 15% (minor), 85% (major).

A small sample of the major isomer was prepared pure by VPC (225C, 20Mcolumn) and was solid. A small sample of the mixture of epimers wasseeded with the crystals, cooled over night at 0C and the materialpartially crystallized. The crystals were filtered, recrystallized twicefrom methanol and vacuum dried, m.p. 43.5 445C. The VPC showed this tobe the major epimer of III which analyzed as follows: mol. wt. 222 (massspectrum):v neat max. 1690 (s), 1388 (s), 1375 (m), 1318 (w), 1240 (w),1145 (m), 1092 (m), 1040 (w), 980 (m), 952 (w), 822 (w), 774 (w), Cm';NMR ('r, ppm,CDCl centered at 7.50 (2H, consisting of an octet),centered at 8.20 1H, consisting of a broad multiplet), 8.81 (3H,singlet, CH 8.97 (3H, doublet, J= 6.5 Hz, CH 8.96 (3H, singlet, CH 9.16(3H, singlet, CH 9.19 (3H, singlet, CH 8.308.75 (8H, complex multiplet,4CH

A small sample of the minor isomer was prepared pure by VPC (225C, 20Mcolumn) and was solid. The sample analyzed as follows: mol. wt. 222(mass spectra); v neat max. 1705 (s), 1395 (m), 1378 (m), 1320 (w), 1197(w), 1158 (w), 1112 (w), 1036 (w), 978 (m), 938 (w), 842 (w), 810 (w),cm); NMR (1', ppm, CDCl centered at 7.17 (1H, septet, J=6.5 Hz, aI-I toC=O), 8.76 (3H, singlet, CH 8.92 (3H, singlet, CH 8.99 (6H, singlet,2C1-1 9.11 (3H, doublet, J=6.5 Hz, CH 7.60 8.85 (10H, complex multiplet,5CH

EXAMPLE XI Base Cologne Formulation There was prepared a citrus colognebase which was used to test the aromatic properties of compounds (I IV).These results are set forth in Examples X11 XV infra: The base had thefollowing composition Benzyl isoeugenol 26 Bergamot oil 286 Geranium oil10 Lavender oil 31 Lemon oil 265 Lime oil 3 Neroli oil 10 Orange bitteroil 138 Orange sweet oil 74 Rosemary oil 31 Sage, clary oil 21 Thyme oil(white) 5 EXAMPLE x11 I Use ofcis-4a,5,6,7,8,8a-hexahydro-3,4a,5,5,8a-pentamethyl- 2(1H)-naphthalenone(I) in a Cologne Base of Ex. XI

Cis-4a,5,6,7,8,8a-hexahydro-3,4a5,5,8apentamethyl-2( lH)-naphthalenone(I) has a strong green woody peppery odor and lasts approximately'two"weeks on a blotter. The addition of 5% of (I) to the above cologne baseadds great strength and lift to the fragrance while contributing adiffusive woody character on dry out. The cologne base .without.(1) isnot as bright nor as pleasing as that with the derivative. This materialalso has fixative properties which produces a better balanced and morepleasing bouquet of the cologne as compared to the cologne base withoutit. The cologne base containing this material produces a fragrance thatlasts approximately twice as long as the cologne without this material.The material has a very intense odor and may generally be used from 0.1%to 25% by weight. Higher concentrations (25% to 90%) may also be usedsuccessfully for unique and special effects.

EXAMPLE XlIl Use ofcis-3,4,4a,5,6,7,8,8a-octahydro-3,4a,5,5,8apentamethyl-2(lH)-naphthalenone (11) in a Cologne Base of Ex.XlCis-3,4,4a,5,6,7,8,8a-octahydro-3,4a,5,5,8 a-pentamethyl-2(lH)-naphthalenone (II) has a strong woody amber odor which lastsapproximately 2 weeks on a blotter. The addition of 5% of this materialto the above cologne base contributes an extremely fresh amber characterto the fragrance. The cologne without (11) is not as fresh nor does ithave the lift and body of that with (11). This material also hasfixative properties which produce a better balanced and more pleasingbouquet of the cologne as compared to the cologne base without it. Thecologne base containing this material produces a fragrance that lastapproximately twice as long as the cologne without this material. Thematerial may generally be used in concentration ranging from 0.1% to 25%by weight. Higher concentrations (25% to 90%) may also be usedsuccessfully for unique and special effects.

EXAMPLE XIV Use ofcis-3,4,4a,5,6,7,8,8a-octahydro-2,4a,8,8,8apentamethyl-l(2H)-naphthalenone(III) in a Cologne Base of Ex. XI

Cis-3,4,4a,5,6,7,8,8a-octahydro-2,4a,8,8,8apentamethyl-1(2H)-naphthalenone(III) has a warm woody odor which lasts approximately 2 weeks on ablotter. The addition of 5% of this material to the above cologne basecontributes lift and strength together with a pleasing woody characteron dry-out. The cologne without (III) is thin and lacks the unique odorqualities contributed by this aroma chemical. This material also hasfixative properties which produces a better balanced and more pleasingbouquet of the cologne as compared to the cologne base without it. Thecologne base containing this material produces a fragrance that lastsapproximately twice as long as the cologne without this material. Thismaterial may be generally used in concentrations ranging from 1% to 25%by weight. Higher concentrations (25% to may be used successfully forunique and special effects.

EXAMPLE XV Use ofcis-decahydro-1,2-epoxy-2,4a,8,8,8a-pentamethylnaphthalene (IV) in aCologne Base of Ex. XI

Cis-decahydro-l ,2-epoxy-2,4a,8,8,8a-pentamethylnaphthalene (IV) has apleasant woody cedar odor which lasts approximately 2 weeks on ablotter. The addition of 5% of this material to the above cologne basecontributes a fresh diffusive woodyness to the fragrance as a whole andadds warmth to the dryout. The cologne without (1V) lacks body and isnot as desirable a fragrance as that with (IV). This material also hasfixative properties which produce a better balanced and more pleasingbouquet of the cologne as compared to the cologne base without it. Thecologne base containing this material produces a fragrance that lastsapproximately twice as long as the cologne without this material.

This material may generally be used in concentrations ranging from 1 to25%. Higher concentrations (25 to 90%) may also be used successfully forunique and special effects.

EXAMPLE XVl Use of the Pentamethyloctalone l as a Sandelwood Component.

The pentamethyloctalone I when compounded with Sandela makes a majorodor contribution to the building of a synthetic sandelwood. This isdemonstrated in the following base:

Pentamethyloctalone l 200 Sandela (Givaudan Corp.) 700 Amyris oil 50 Am.Cedarwood oil 50 The addition of 1 produces a fatty-woody characterwhich is observed in sandelwood. It contributes a more naturalsandelwood note to the above formulation and is considered important tothe formulation of a synthetic sandelwood base. In such a formulation, 1may be used over a range of 5% to 60% by weight.

EXAMPLE XVII Use of the Pentamethyl-Z-decalone II, thePentamethyl-l-decalone Ill and the Epoxypentamethyldecalin IV asSandelwood Components.

The pentamethyl-2-decalone ll, the pentamethyl-ldecalone III and theepoxypentamethyldecalin IV are not as outstanding by themselves aspentamethyloctalone l in the above synthetic sandelwood formulation.However, they do contribute unique notes to this type of formulationwhen used together with l. The following formulae demonstrates:

A B C Pentamethyloctalone l 200 200 200 Sandela 600 600 600 Amdyris oil50 O 50 Ce arwood oil (Am.) 50 50 S0 Epoxypentamethyldecalin IV 100Pentamethyl-l-decalone Ill 100 Pentamethyl-Z-decalone III 100 I000 l000l000 2. A process for the preparation of the compound of claim 1, whichcomprises oxidizing cisdihydrothujopsene with an oxidant selected fromthe group consisting of alkali metal dichromates and alkyl chrornates inan anhydrous medium.

3. A process of claim 2 wherein the medium is an alkanoic acidandanhydride.

4. A process of claim 2 wherein the oxidant is sodium or potassiumdichromate or t-butyl chromate.

1. A COMPOUND OF THE STRUCTURE
 2. A PROCESS FOR THE PREPARATION OF THECOMPOUND OF CLAIM 1, WHICH COMPRISES OXIDIZING CIS-DIHYDROTHUJOPSENEWITH AN OXIDANT SELECTED FROM THE GROUP CONSISTING OF ALKALI MEALDICHROMATES AND ALKYL CHROMATES IN AN ANHYDROUS MEDIUM.
 3. A process ofclaim 2 wherein the medium is an alkanoic acid and anhydride.
 4. Aprocess of claim 2 wherein the oxidant is sodium or potassium dichromateor t-butyl chromate.